US5079378A - Preparation of diaryliodonium salt photoinitiators having long chain ester groups concatenated with aryl groups - Google Patents
Preparation of diaryliodonium salt photoinitiators having long chain ester groups concatenated with aryl groups Download PDFInfo
- Publication number
- US5079378A US5079378A US07/558,627 US55862790A US5079378A US 5079378 A US5079378 A US 5079378A US 55862790 A US55862790 A US 55862790A US 5079378 A US5079378 A US 5079378A
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- US
- United States
- Prior art keywords
- carbon atoms
- aryl
- diaryliodonium
- ester
- salt
- Prior art date
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- Expired - Fee Related
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- 125000005520 diaryliodonium group Chemical group 0.000 title claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 6
- 125000004185 ester group Chemical group 0.000 title description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- -1 metal halide anion Chemical class 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910001507 metal halide Inorganic materials 0.000 claims description 7
- LRIUKPUCKCECPT-UHFFFAOYSA-N [hydroxy(phenyl)-$l^{3}-iodanyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OI(O)C1=CC=CC=C1 LRIUKPUCKCECPT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 3
- YCADXCSWOBLSPP-UHFFFAOYSA-N 1,3-bis(ethenoxy)-2-methylpropane Chemical compound C=COCC(C)COC=C YCADXCSWOBLSPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 2
- 150000002118 epoxides Chemical class 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 claims 1
- 238000012719 thermal polymerization Methods 0.000 claims 1
- 239000012955 diaryliodonium Substances 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FSXLZUKMPRDBFO-UHFFFAOYSA-N (2-hydroxy-6-iodophenyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=C(O)C=CC=C1I FSXLZUKMPRDBFO-UHFFFAOYSA-N 0.000 description 3
- VXTYHHOLNULIMV-UHFFFAOYSA-N 2-(1-octadecylcyclohexa-2,4-dien-1-yl)oxyacetic acid Chemical compound CCCCCCCCCCCCCCCCCCC1(CC=CC=C1)OCC(=O)O VXTYHHOLNULIMV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- KTNLYTNKBOKXRW-UHFFFAOYSA-N phenyliodanium Chemical compound [IH+]C1=CC=CC=C1 KTNLYTNKBOKXRW-UHFFFAOYSA-N 0.000 description 3
- ASOPLEJLONXGSD-UHFFFAOYSA-N (4-octadecoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 ASOPLEJLONXGSD-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 2
- ZEKFPPPIHZBYDN-UHFFFAOYSA-N 2-(1-tetradecylcyclohexa-2,4-dien-1-yl)oxyacetic acid Chemical compound CCCCCCCCCCCCCCC1(CC=CC=C1)OCC(=O)O ZEKFPPPIHZBYDN-UHFFFAOYSA-N 0.000 description 2
- VVVMWBWXKNRXDI-UHFFFAOYSA-N 2-ethylideneoxirane Chemical compound CC=C1CO1 VVVMWBWXKNRXDI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acenaphthylene Chemical compound C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthalene Natural products C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910001545 sodium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- WDNZXSXESBLVBD-UHFFFAOYSA-N tetradecyl 2-phenoxyacetate Chemical compound CCCCCCCCCCCCCCOC(=O)COC1=CC=CC=C1 WDNZXSXESBLVBD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Definitions
- Diaryliodonium salts are used as efficient photoinitiators for cationic polymerization.
- the instant invention relates generally to the synthesis of diaryliodonium salts possessing aliphatic ester groups of differing lengths and, specifically, to novel diaryliodonium salts in which long chain ester groups are attached to the aryl groups. More precisely, diaryliodonium salts of the instant invention possess aryl and aliphatic ester groups bonded to iodine which together comprise an aggregate of more than 20 carbon atoms.
- diaryliodonium salts having the structure Ar--I + --Ar MX n - , where Ar are aryl groups and MX n - represents the metal halide anion, serve as efficient photoinitiators for cationic polymerization.
- aryl groups are defined as consisting of aromatic groups or arylalkyl groups containing from 6 up to, but not exceeding, 20 carbon atoms. Quite matter of factly, such salts as would contain more carbon atoms are specifically excluded.
- diaryliodonium salts could be enhanced if the total number of carbon atoms within the groups bonded to iodine exceeded 20.
- diaryliodonium salts in which long chain ester groups are attached to the aryl groups, thus providing an aggregate (aromatic-aliphatic) number of carbon atoms in the desired quantities.
- incorpororation of the long chain ester functions onto the aryl groups does indeed confer enchanced solubility to these salts compared to their lower molecular weight counterparts, a characteristic hereinafter demonstrated.
- the R groups represent hydrogen, alkyl, halogen or aryl.
- the values n represent integers such that the combined number of carbon atoms included by the entire moiety attached to the positively charged iodine atom is greater than 20.
- MX represents a metal halide and X - comprises those complex (metal) halide anions such as BF 4 --, PF 6 --, AsF 6 --, SbF 6 --, as well as anions of strong protonic acids such as ClO 4 --, CF 3 SO 3 --, FSO 3 --, CH 3 SO 3 --, and C 4 F 9 SO 3 --.
- Several examples of such compounds are: ##STR2##
- the initiators described in this disclosure may be used to carry out the photoinitiated polymerization of such cationically polymerizable monomers as momo, di and polyfunctional epoxides such as bisphenol-A diglycidyl ether, butanedioldiglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycylohexane carboxylate, phenol novolac epoxides, poly (1,2- butadiene oxide), epoxidized soybean oil, epoxidized linseed oil; vinyl ethers, such as diethyleneglycol divinyl ether, triethyleneglycol divinyl ether, dicyclohexanediol divinyl ether, 1,4-butandiol divinyl ether; vinyl hydrocarbon monomers including styrene, alpha-methyl styrene, divinyl benzene, 1,3-diisopropen
- Heterocyclic mononers such as N-vinyl carbazole, oxetane, trioxane, 1,3-dioxolane, and tetrahydrofuran can also be polymerized using these photoinitiators.
- the most useful, but not exclusive, application of these photoinitiators are in formulations intended for use as ultraviolet light (UV) curable coatings, adhesives and sealants.
- UV ultraviolet light
- the photoinitiators are also useful for photoimaging purposes as in the fabrication of photoresists for electrical and electronic applications.
- diaryliodonium salts are useful in combination with copper cocatalysts or free radical initiators as thermal initiators for the above monomers and polymers.
- These initiator/coinitiator combinations have utility in a wide variety of applications including molding. pulltrusion, composites, encapsulants, adhesives and foams.
- the salt was an excellent photoinitiator for the polymerization of 4-vinyl cyclohexene dioxide. It is also soluble in epoxidized linseed oil, epoxidized soybean oil and in poly(1,2-butadiene oxide) and can be used to photopolymerize these substances.
- the oil was diluted with 50 ml acetone; and, 5.18 g sodium hexafluoroantimonate was added.
- Sodium tosylate precipitated on stirring for one hour.
- the acetone was evaporated on a rotary evaporator and the remaining mixture of oil and crystals poured into 300 ml distilled water.
- the product a light tan colored semisolid, was washed several times with water and on standing tended to crystallize. There were obtained 21.4 g of product.
- the crude iodonium salt was very active as a photoinitiator and was dissolved as a 0.5% solution in 4-vinylcyclohexene dioxide.
- OPPA is a superior photoinitiator.
- This photoinitiator contains an ester linkeage attached to the aromatic ring as well as possessing more than 20 carbon atoms in the side chain.
- DP diphenyliodonium hexafluoroantimonate
- 4-octadecyloxyphenyl) phenyliodonium hexafluoroatimonate analogs are not soluble in the monomer and for this reason fail to cure when these solutions are irradiated.
- OPPA is soluble in alpha-methylstyrene, while both DP and OPP are not.
- Alpha-methylstyrene is a well known cationically polymerizable monomer. In this case, only OPPA could be employed to carry out its cationic polymerization.
Abstract
A highcarbon-containing diaryliodonium initiator for cationic polymerization which possesses enhanced solubility characteristics over conventional diaryliodonium initiators. By the disclosed process, a novel photo/thermal initiator is obtained which is uniquely characterized by the concatenation of a long chain ester with an aryl group, resulting in a total number of carbon atoms in the entire moiety attached to the iodine atom in excess of 20.
Description
1. Field of the Invention
Diaryliodonium salts are used as efficient photoinitiators for cationic polymerization. The instant invention relates generally to the synthesis of diaryliodonium salts possessing aliphatic ester groups of differing lengths and, specifically, to novel diaryliodonium salts in which long chain ester groups are attached to the aryl groups. More precisely, diaryliodonium salts of the instant invention possess aryl and aliphatic ester groups bonded to iodine which together comprise an aggregate of more than 20 carbon atoms.
2. Discussion of Relevant Art
A search of the patent literature, as well as the professional journals, reveals that diaryliodonium salts having the structure Ar--I+ --Ar MXn -, where Ar are aryl groups and MXn - represents the metal halide anion, serve as efficient photoinitiators for cationic polymerization. In U.S. Pat. No. 4,090,936, issued to Barton for PHOTOHARDENABLE COMPOSITIONS, aforementioned diaryliodonium salts are disclosed wherein the aryl groups are defined as consisting of aromatic groups or arylalkyl groups containing from 6 up to, but not exceeding, 20 carbon atoms. Quite matter of factly, such salts as would contain more carbon atoms are specifically excluded. In a patent recently issued to the instant inventor and incorporated herein by reference: NON-TOXIC ARYL ONIUM SALTS, UV CURABLE COATING COMPOSITIONS AND FOOD PACKAGING USE (U.S. Pat. No. 4,882,201), the invention of non-toxic photoinitiators comprising diaryliodonium salts which possess alkoxy groups of differing lengths is taught. However, no mention is made of similar diaryliodonium salts containing other functional groups having long carbon chains. Most notably, diaryliodonium salts with ester (aliphatic) groups attached to the aryl moieties, together exceeding 20 carbon atoms, are not described therein, nor in the patent or chemical literature.
The instant inventor believed that the organic solubility of diaryliodonium salts could be enhanced if the total number of carbon atoms within the groups bonded to iodine exceeded 20. Quite unexpectedly, he discovered that it is possible to prepare, in good to excellent yield, diaryliodonium salts in which long chain ester groups are attached to the aryl groups, thus providing an aggregate (aromatic-aliphatic) number of carbon atoms in the desired quantities. Incorporation of the long chain ester functions onto the aryl groups does indeed confer enchanced solubility to these salts compared to their lower molecular weight counterparts, a characteristic hereinafter demonstrated.
A general process for the synthesis of the diaryliodonium salts of the instant invention is: ##STR1##
In the above process, the R groups represent hydrogen, alkyl, halogen or aryl. The values n represent integers such that the combined number of carbon atoms included by the entire moiety attached to the positively charged iodine atom is greater than 20. MX represents a metal halide and X- comprises those complex (metal) halide anions such as BF4 --, PF6 --, AsF6 --, SbF6 --, as well as anions of strong protonic acids such as ClO4 --, CF3 SO3 --, FSO3 --, CH3 SO3 --, and C4 F9 SO3 --. Several examples of such compounds are: ##STR2##
The initiators described in this disclosure may be used to carry out the photoinitiated polymerization of such cationically polymerizable monomers as momo, di and polyfunctional epoxides such as bisphenol-A diglycidyl ether, butanedioldiglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycylohexane carboxylate, phenol novolac epoxides, poly (1,2- butadiene oxide), epoxidized soybean oil, epoxidized linseed oil; vinyl ethers, such as diethyleneglycol divinyl ether, triethyleneglycol divinyl ether, dicyclohexanediol divinyl ether, 1,4-butandiol divinyl ether; vinyl hydrocarbon monomers including styrene, alpha-methyl styrene, divinyl benzene, 1,3-diisopropenylbenzene, and acenaphthalene. Heterocyclic mononers such as N-vinyl carbazole, oxetane, trioxane, 1,3-dioxolane, and tetrahydrofuran can also be polymerized using these photoinitiators. The most useful, but not exclusive, application of these photoinitiators are in formulations intended for use as ultraviolet light (UV) curable coatings, adhesives and sealants. The photoinitiators are also useful for photoimaging purposes as in the fabrication of photoresists for electrical and electronic applications.
In addition, the same diaryliodonium salts are useful in combination with copper cocatalysts or free radical initiators as thermal initiators for the above monomers and polymers. These initiator/coinitiator combinations have utility in a wide variety of applications including molding. pulltrusion, composites, encapsulants, adhesives and foams.
The above is a general synthesis which can be expanded to cover a large family of such photoinitiators. This includes also hexafluorophosphate as well as hexafluoroantimonate containing salts. The photoinitiators are very reactive and, because of their high molecular weight and hydrocarbon-like character, are probably non-toxic. The reader is once again referred to U.S. Pat. No. 4,882,201, issued to the instant inventor.
The following accounts of actual experiments are given by way of demonstration and not of limitation. ##STR3##
Initially, 208 g (1.0 mol, 98%) of iodobenzene were placed in a 1 L three necked flask fitted with an addition funnel, condenser, thermometer and paddle stirrer. Dropwise, 52 g. (2.4 mol) 35% peracetic acid were added, with stirring. The temperature was maintained between 40° and 45° C. during the addition using a water bath. After addition was complete, the yellow solution was maintained at 40° C. for one hour. Within 20 minutes a precipitate of iodosobenzene diacetate began to form and the solution became quite thick. Maintaining the reaction mixture at 40° C., there were added 298 g (1.57 mol) p-toluenesulfonic acid monohydrate in portions. As reaction proceeded, the solution became preceptively more fluid, then once again thixotropic as the product [hydroxy(tosyloxy)iodo]benzene precipitated. The reaction temperature was maintained at 40° C. for two hours after addition had been completed. The product was isolated by suction filtration, washed with water and air dried; thus, were obtained 217.3 g of the product (yields generally ranged from 84 to 97%).
Into a 500 ml round bottom flask there were placed 15.2 g (0.1 mol) phenoxyacetic acid, 27 g (0.1 mol) 1-octadecanol, 110 ml toluene and 0.5 g p-toluenesulfonic acid monohydrate. The reaction was heated to reflux and the water separated using a Dean Stark trap. The reaction was allowed to proceed for 14 hours during which the theoretical amount of water (1.8 g) collected in the trap. Using the trap, the toluene was removed and the oil which remained cooled. The product ester crystallized on cooling. Quantitative yield of 41 g of the product was obtained having a m.p. of 50°-52° C. and molecular weight (MW) of 404 g/mol (C26 H44 O3).
The above experiment was repeated using one mole each of 1-octadecanol and phenoxy acetic acid. There was also added 1 g p-toluene sulfonic acid and 250 ml toluene. The theoretical amount of water (18 ml) was obtained within three hours at reflux. The remaining toluene was removed on a rotary evaporator, giving a pale yellow oil.
To a 100 ml Erlenmeyer flask, there were added 8.08 g (0.02 mol) of the above ester, 7.84 g (0.02 mol) hydroxytosyloxyiodobenzene, 20 ml methylene chloride and 5 ml glacial acetic acid. This reaction mixture was placed in a water bath and heated for two hours to complete the reaction. Next, the reaction mixture was gravity filtered and the solvent removed from the filtrate using a rotary vacuum evaporator. A pale yellow oil remained. To the oil there was added ≈40 ml acetone and 5.18 g sodium hexafluoroantimonate. Immediate metathesis took place with the formation of a precipitate of sodium tosylate as the reaction proceeded. After 15 min. stirring, the reaction mixture was gravity filtered and the acetone removed on a rotary evaporator. On cooling, partial crystallization of the product occured. When water was added to the semisolid product, the entire reaction mixture crystallized to give, after drying overnight at ≈40° C. in vacuuo, a pale yellow product. Yield was 10.2 g (60% theory) of M.W. 845 g/mol (C32 H48 O3 ISbF6), m.p. 45°-47° C. Solvents comprised i-propanol, toluene, acetone and cyclohexane. The compound was purified by trituration of an i-propanol solution with distilled water.
The salt was an excellent photoinitiator for the polymerization of 4-vinyl cyclohexene dioxide. It is also soluble in epoxidized linseed oil, epoxidized soybean oil and in poly(1,2-butadiene oxide) and can be used to photopolymerize these substances.
Scale-up of the above reaction was carried out using 80.8 g (.2 mol) of the ester and 78.4 g (0.2 mol) of hydroxytosyloxyiodobenzene, 150 ml methylene chloride and 50 ml glacial acetic acid. The mixture was heated to reflux (40° C.) for two hours. The turbid solution was filtered and the solvent removed under vacuum. Then, 300 ml acetone was added, followed by 51.8 g (0.2 mol) sodium hexafluoroantimonate. The reaction was allowed to stir for one hour and was then filtered. On removal of the actone and the addition of a small amount of distilled water, partial crystallization took place. The product, a pale yellow oil was mixed with water and filtered. A semisolid product was obtained which was recrystallized by dissolution in hot isopropanol. Crystallization took place by cooling on ice and the product was isolated by filtration. There were obtained 107 g of the desired product.
The above reaction was repeated with a replacement of the NaSbF6 with 3.68 g KPF6, to prepare the corresponding iodonium hexafluorophosphate salt. After 1 hour at 40° C., the potassium tosylate was filtered off. However, the product tended to cocrystallize during the filtration. The product (10.4 g) was isolated on addition of distilled water to the filtrate. Higher yields could be obtained through direct addition of water to the acetone solution. A 3 mil film of a 1% solution of the above photoinitiator, dissolved in 4-vinylcyclohexene dioxide, cured after a 5 second exposure to ultraviolet lighting using a UVEXUS Spot cure apparatus.
Into a 500 ml three neck flask equipped with a magnetic stirrer, reflux condenser and Dean Stark trap were placed 15.2 g (0.1 mol) phenoxyacetic acid, 21.6 g (0.1 mol) 1-tetradecanol, 1 g p-toluenesulfonic acid monohydrate and 100 ml toluene. The reaction mixture was brought to reflux and held at the temperature for four hours. The theoretical amount of water was collected in the trap. The toluene was distilled off and the product crystallized on standing.
As in the first example, there were placed into a 150 ml Erlenmeyer flask, 20 ml methylene chloride, 7.84 (0.02 mol) hydroxytosyloxy iodobenzene, 10 ml glacial acetic acid and 6.96 g (0.02) mol 1-tetradecyl phenoxyacetate. The mixture was heated to 40° C. in a water bath. Reaction required approximately one hour during which the bulk of the insoluble [hydroxy(tosyloxy)iodo]benzene dissolved. The methylene chloride was removed using a rotary evaporator and to the pale yellow oil was added 30 ml acetone and 5.18 g (0.02 mol) sodium hexafluoroantimonate. Immediate precipitation of sodium tosylate occurred. The salt was removed by suction filtration and the solvent removed from filtrate on a rotary evaporator. The remaining pale yellow oil (12.9 g) was washed with two 100 ml portions of distilled water. One percent solutions of this photoinitiator when dissolved in 4-vinyl cyclohexene dioxide and spread as 1 mil films on glass plates gave cured, tack-free films in 5 seconds when irradiated with a G.E. H3T7 medium pressure mercury arc lamp ballasted at 100 Watts. When a one percent solution of the above photoinitiator was prepared in triethylene glycol divinyl ether, the mixture cured to hard insoluble films after exposure for one second as described above.
Combined were 38.6 g (0.1 mol) cholesterol (C27 H34 O), 15.2 g (0.1 mol) phenoxyacetic acid, 0.5 g p-toluenesulfonic acid monohydrate and 70 ml toluene. The reaction mixture was heated to reflux for five hours during which 1.8 g water was collected in a Dean Stark trap. There were isolated after removal of the toluene, 52 g (100% yield) of the ester.
To 7.88 g (0.02 mol) [hydroxy(tosyloxy)iodo]benzene there were added 10.77 g (0.02 mol) of 3-cholesterylphenoxyacetate, 25 ml methylene chloride and 5 ml glacial acetic acid. The reaction mixture was stirred and heated to 40° C. (reflux) for one hour during which all of the solid [hydoxy(tosyloxy)iodo]benzene dissolved. On initial mixing of the components at room temperature a characteristic green color developed as the reaction proceeded. The methylene chloride was removed on a rotary evaporator leaving a yellow-brown oil.
The oil was diluted with 50 ml acetone; and, 5.18 g sodium hexafluoroantimonate was added. Sodium tosylate precipitated on stirring for one hour. After removing the sodium tosylate by filtration, the acetone was evaporated on a rotary evaporator and the remaining mixture of oil and crystals poured into 300 ml distilled water. The product, a light tan colored semisolid, was washed several times with water and on standing tended to crystallize. There were obtained 21.4 g of product. The crude iodonium salt was very active as a photoinitiator and was dissolved as a 0.5% solution in 4-vinylcyclohexene dioxide. Exposure of a one mil film of this mixture to a G.E. H3T7 medium pressure mercury arc lamp ballasted at 200W gave a cured film after a one second irradiation. The iodonium salt was recrystallized using a mixture of isopropanol and water as a recrystallization solvent. The product was a pale yellow crystalline solid (yield 11 g).
The examples disclosed herein are directed to but a few compounds of this new class of diaryliodonium salt photo and thermal initiators. The general description preceeding these examples provides clear insight to the preparation and use of the salts disclosed in the instant invention. It will be observed that these new initiators also have excellent compatability with even such nonpolar monomers as epoxidized oils and poly (1,2-butadiene oxide). These and other utility factors will be discernable by those of ordinary skill practicing the invention and whose interest is further stimulated by the following evidence regarding the solubility and reactivity of the new initiators.
The following experimental activities were carried out to further evidence solubility and reactivity of the diaryliodonium salts of the present invention, as compared to simple diaryliodonium salts described in the earlier art (cf. J. V. Crivello and J. L. Lee, U.S. Pat. No. 4,882,201, Nov. 21, 1989, "Non-Toxic Aryl Onium Salts, UV Curable Coating Compositions and Food Packaging Use." an J. V. Crivello and J. L. Lee, U.S. Pat. No. 4,683,317, Jul. 28, 1987, "Photopolymerizable Organic Compositions and Diaryliodonium Salts Used Therein").
There were prepared one percent (1%) by weight mixtures of the following salts in 2-methyl-1,3-propanediol divinyl ether: diphenyliodonium hexafluoroantimonate (DP), [4(1-octadecylphenoxyacetate)]phenyl iodonium hexafluoroantimonate (OPPA) and (4-octadecyloxyphenyl)phenyl iodonium hexafluoro hexafluoroantimonate (OPP). The three solutions were coated as one (1.0) mil films onto glass plates and exposed to a General Electric H3T7 medium pressure mercury arc lamp at a distance of six inches. The minimum irradiation time required to produce a tack-free coating was recorded.
______________________________________ PHOTOINITIATOR TACK-FREE TIME (sec) ______________________________________ DP >50 OPPA 1.0 OPP >30 ______________________________________
Clearly, in this rather typical cationically polymerizable monomer, OPPA is a superior photoinitiator. This photoinitiator contains an ester linkeage attached to the aromatic ring as well as possessing more than 20 carbon atoms in the side chain. In contrast, the diphenyliodonium hexafluoroantimonate (DP) and even the (4-octadecyloxyphenyl) phenyliodonium hexafluoroatimonate analogs are not soluble in the monomer and for this reason fail to cure when these solutions are irradiated.
In another series of tests, it was found that OPPA is soluble in alpha-methylstyrene, while both DP and OPP are not. Alpha-methylstyrene is a well known cationically polymerizable monomer. In this case, only OPPA could be employed to carry out its cationic polymerization.
Thus, the superiority of the photoinitiators of this invention as compared to those of the earlier art in the cure of nonpolar monomers and oligomers is clearly demonstrated.
Claims (7)
1. A process for making diaryliodonium salt photo/thermal initiators for cationic polymerization which have solubilities greater than diaryliodonium salts possessing carbon groups of 20 carbon atoms and less, said process comprising the steps of:
a) esterfying a monoaryl acid to produce a monoaryl ester of the form ##STR13## R representing hydrogen, aryl, alkyl or a halide; and b) reacting said ester with hydroxy(tosyloxy)iodobenzene in the presence of an organic solvent and thereafter with a metal halide to produce said diaryliodonium salt comprising a long chain ester function concatenated with an aryl group of said acid in said esterfying step with more than 20 carbon atoms in said concatenated function/group and of the form: ##STR14## wherein n is such that the total number of carbon atoms is greater than 20, and X- is a complex metal halide anion.
2. The process of claim 1 wherein X- is a complex metal halide anion such as BF4 --, PF6 --, AsF6 --, and SbF6 --.
3. The process of claim 2 wherein X- further comprises anions of strong protonic acids.
4. A diaryiodonium salt for photo/thermal initiation of cationic polymerization of such monomers as mono,di-and polyfuctional epoxides, said salt characterized by the general formula: ##STR15## where: R is hydrogen, aryl, alkyl or an halide;
n is an integer such that the total number of carbon atoms included by the entire moiety appended to the iodine atom is greater than 20; and
S- is a complex metal halide anion.
5. The diaryliodonium salt of claim 4 wherein X- further comprises a complex halide anion of a strong protonic acid.
6. A photo/thermal polymerization initiator that is soluble in 2-methyl-1,3-propanediol divinyl ether and alphamethylstyrene monomers and is characterized as a diaryliodonium group having contatenated therewith an aliphatic group wherein a total of 21 or more carbon atoms comprise the aryl/aliphatic groupings.
7. A method for making the initiator of claim 6 comprising reacting a monoaryl ester of the form ##STR16## n being an integer such that the ester contains at least 15 carbon atoms, R representing hydrogen, aryl, alkyl or a halide, with [hydroxy(tosyloxy)iodo]benzene in the presence of an organic solvent and a metal halide capable of imparting a complex halide anion to said initiator.
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